JP2012514611A - Functional materials for printed electronic components - Google Patents

Abstract

The present invention relates to metallic organoaluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complexes and mixtures thereof comprising at least one ligand from the oximate class for electronic components The present invention relates to a printable precursor and a manufacturing method. The invention further relates to a corresponding printed electronic component, preferably a field effect transistor.

Description

  The present invention relates to aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin-containing precursors for electronic components, and a manufacturing method. Furthermore, the present invention relates to corresponding printed electronic components and manufacturing methods suitable for them.

  In order to use print electronics in mass applications (eg RFID (= radio frequency identification) chips in individual packages) it is desirable to use established mass printing processes. In general, printed electronic components and systems consist of a plurality of material parts such as conductors, for example for contacts, semiconductors, for example as active materials, insulators, for example as barrier layers.

  The manufacturing process usually consists of a vapor deposition stage, i.e. applying the respective material to a support material (substrate) and subsequent process stages, thereby ensuring the desired properties of the material. For high volume handling, for example roll to roll processing, it is desirable to use a flexible substrate (film or foil). Previous processes for manufacturing printed circuits have essential advantages, but also have drawbacks:

Prior art (see WO 2004086289): Here, a conventional Si logic unit and an additional structured part, or a hybrid of printed parts (for example a metal antenna in the case of an RFID chip) is assembled in a high-cost manner . However, this process is considered overly complex for actual mass production purposes.

Organic materials (see DE 19851703, WO 2004063806, WO 2002015264) : These systems are printed electronic components based on polymers from the liquid phase. These systems are distinguished from solutions by a simple process compared to previously known materials (prior art). The only process step to be considered here is solvent drying. However, the achievable efficiencies, for example in the case of semiconductor materials or conductive materials, are limited by the properties typical of the material, for example by the so-called hopping mechanism, for example charge carrier mobility <10 cm ² / Vs. This limitation affects the applicability: Print transistor efficiency increases with the degree of semiconductor channel reduction, which currently cannot be printed smaller than ˜40 μm using high volume processes. A further limitation of the technology is the sensitivity of organic materials to ambient conditions. This complicates process performance during manufacturing and in some cases results in a shorter life of the printed part.

Inorganic materials : Due to different intrinsic properties (eg stability to UV-induced degradation) compared to organic materials, this class of materials generally has the potential for increased efficiency in use in printed electronics.

In principle, two different methods can be used in this area:
i) Preparation from the gas phase without additional process steps: in this case it is possible to produce very well insulating thin layers, but with the associated high-cost vacuum technique and slow layer formation, Limited use in the mass market.

ii) Wet chemical preparation starting from a precursor material, which is applied from the liquid phase, for example by spin coating or printing (see US 6867081, US 6867422, US 2005/0009225). In some cases, a mixture of an inorganic material and an organic matrix is also used (see US 2006/0014365).

  In order to ensure consistent electrical properties of the layers produced, process steps beyond solvent evaporation are usually necessary. In all cases, it is necessary to produce a form having run into one another regions where the precursor from the wet phase is further converted into the desired active material. This produces the desired functionality (in the case of semiconductors: high charge carrier mobility). Thus, processing takes place at temperatures> 300 ° C., which makes it impossible to use this process for film coating.

  Examples using precursor materials for MgO are, for example, Stryckmans et al. Thin Solid Films 1996, 283, 17 (from magnesium acetylacetonate above 260 ° C.) or Raj et al. Crystal Research and Technology 2007, 42 867 (from magnesium acetate from 300 ° C. in multiple stages). In both cases, spray pyrolysis is used for layer deposition from the gas phase. In this case, the solution is sprayed onto a heated substrate (higher than 400 ° C.) and optionally post-treated at still higher temperatures. Due to the required high temperature, it cannot be used in the printing process.

Examples using soluble ZrO ₂ precursor materials are described in Ismail et al. Powder Technology 1995, 85, 253 (from zirconium acetylacetonate over multiple steps at 200-600 ° C.).
Examples using soluble HfO ₂ are known, for example, from Zherikova et al. Journal of Thermal Analysis and Calorimetry 2008, 92, 729 (from hafnium acetylacetonate for long periods at T = 150-500 ° C.).

  Beta-diketonates, such as zirconium and hafnium acetylacetonates, are used in layer deposition from the gas phase by chemical vapor deposition (CVD). Here, the compound is vaporized in a high vacuum and deposited on a heated substrate (higher than 500 ° C.). Conversion to oxide ceramics takes place via a variety of discontinuous intermediates, but these are not used as functional materials. In this way, high temperatures are required to ensure a certain reaction, which makes it impossible to use in the printing process.

  For the preparation of indium tin oxide (abbreviated “ITO”), the precursor used is, for example, a sol of tin and indium salts in the presence of an amine such as ethanolamine (Prodi et al Journal of Sol-Gel Science and Technology 2008, 47, 68). The conversion to oxide is carried out here at a temperature higher than 500-600 ° C. The required high temperature makes it unusable in the printing process for temperature sensitive substrates.

  The preparation of semiconductor oxide ceramics that are amorphous is noteworthy (K. Nomura et al. Nature 2004, 432, 488-492; H. Hosono Journal of Non-Crystalline Solids 2006, 352, 851- 858; T. Kamiya et al. Journal of Display Technology 2009, 5, 273-288). The indium-gallium-tin-zinc-oxygen phase system is now investigated in detail. Typical examples are indium gallium zinc oxide (abbreviated “IGZO”) and zinc tin oxide (abbreviated “ZTO”), and indium zinc tin oxide (abbreviated “IZTO”). Is).

  The deposition of the semiconductor layer is usually done via the gas phase, but solution-based processes are also known. However, the sol used here requires a relatively high processing temperature. Zinc tin oxide can be obtained from anhydrous tin (II) chloride or tin (II) acetate and zinc acetate hexahydrate in the presence of a base such as ethanolamine. Conversion to oxide (with oxidation of tin components) is at least 350 ° C. (D. Kim et al. Langmuir 2009, 25, 11149-11154) depending on the reaction capacity during calcination in air Alternatively, it is carried out at 400 to 500 ° C. (SJ Seo et al. Journal of Physics D: Applied Physics, 2009, 42, 035106). Indium zinc tin oxide is obtained from anhydrous indium chloride, zinc chloride and tin (II) chloride in ethylene glycol by reaction with sodium hydroxide solution and subsequent calcination at 600 ° C. (DH Lee et al. Journal of Materials Chemistry 2009, 19, 3135-3137).

  The use of these conventional precursors for printed circuit manufacturing is limited in their applicability in mass production for mass printing applications.

  The object of the present invention was therefore to provide an inorganic material in which the dielectric properties, semiconductor properties and conductive properties can be adjusted on the one hand by the material composition and on the other hand by the method for preparing the printing material. To this end, the aim is to develop a material system that maintains the advantages of inorganic materials. It should be possible to process the material from the wet phase by a printing process. In each case, the electronic efficiency of the desired material on the plane, and the flexible substrate must be manufactured using process steps that require only a low input of energy.

  Surprisingly, a novel organometallic precursor material is prepared and applied to the surface and then to a dielectrically active material at low temperature, ie an insulating material, and also electrically to a semiconducting or conducting material A process to be converted was developed. The layers produced in the process are distinguished by surface properties that are advantageous for the printing process.

Drawing Index The invention is described in more detail below with reference to a number of exemplary embodiments (see FIGS. 1-8b).
FIG. 1 shows the dependence of dynamic viscosity on precursor content for a hafnium hydroxo [2- (methoxyimino) propanoate] solution in methoxyethanol. Measurements were made under standard environmental conditions (DIN 50 014-23). FIG. 2 shows a thermogravimetric analysis of zirconium and hafnium hydroxo [2- (methoxyimino) propanoate] in oxygen (1 = curve of the zirconium complex, 2 = curve of the hafnium complex). By reducing the relative mass as a function of temperature, one can conclude on the essential reaction temperature.

FIG. 3 shows in each case X of a film of the invention comprising zirconium oximate in 2-methoxyethanol / 2-butanol by spin coating on a silicon substrate and processing for 30 minutes at various temperatures. It is a figure which shows the analysis by a line photoelectron spectroscopy (XPS). (A = Zr3d signal, b = N1s signal, c = C1s signal, 1 = no further processing, 2 = processing at 200 ° C., 3 = processing at 250 ° C.) The XPS spectrum shows the elements present in the sample and Conclusions can be made about the oxidation state, as well as the mixing ratio. Thus, it can be shown that zirconium oxide is present in the film after processing.

FIG. 4 shows in each case X-ray photon spectroscopy of a film of the invention comprising magnesium oximate in 2-methoxyethanol by spin coating on a silicon substrate and processing for 30 minutes at various temperatures. It is a figure which shows the analysis by (XPS). In some measurements, the surface was cleaned by sputtering in the measurement chamber. (A = Mg1s signal, b = O1s signal, c = C1s signal, 1 = processing at 210 ° C. + sputtering, 2 = processing at 450 ° C., 3 = processing at 450 ° C. + sputtering) Sample by XPS spectrum Conclusions can be made about the elements and oxidation states present therein, as well as the mixing ratio. Thus, it can be shown that magnesium oxide is present in the film after processing.

FIG. 5 shows in each case X of a film of the invention comprising hafnium oximate in 2-methoxyethanol / 2-butanol by spin coating on a silicon substrate and processing at various temperatures for 30 minutes. It is a figure which shows the analysis by a line photon spectroscopy (XPS). (A = Hf4f signal, b = N1s signal, c = C1s signal, 1 = no processing, 2 = processing at 200 ° C., 3 = processing at 250 ° C.) Elements and oxidation present in the sample by XPS spectrum One can conclude about the condition as well as the mixing ratio. Thus, it can be shown that hafnium oxide is present in the film after processing.

FIG. 6 shows a diagram of the structure of the dielectric layer of the present invention. (1 = conductor-gold or aluminum, 2 = dielectric-zirconium oxide, 3 = conductor-gold or aluminum, 4 = substrate / insulator-glass). FIG. 7 shows a current / voltage curve for the determination of the breakdown voltage in the component from FIG. The current / voltage curve shows the typical shape of the dielectric; the breakdown voltage can be determined thereby as an important parameter of the material.

FIG. 8a : Diagram showing the structure of a thin film field effect transistor (1 = conductor (drain and source), 2 = semiconductor, 3 = dielectric, 4 = conductor (gate)). The component has electrodes in a top-contact arrangement. FIG. 8b : Diagram showing the structure of a thin film field effect transistor (1 = semiconductor, 2 = conductor (drain and source), 3 = dielectric, 4 = conductor (gate)). The part has electrodes in a bottom-contact arrangement.

  Accordingly, the present invention is a precursor for coating electronic components and contains at least one ligand from the oximate class, organometallic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium And / or a tin complex or a mixture thereof. If the reaction is carried out in a suitable manner, the precursor can also be prepared without alkali metals. This can be advantageous for use in electronic components since alkali metal-containing residues can have an adverse effect on electronic properties. These elements can have an unfavorable effect on the properties as foreign atoms in the crystal.

In a preferred embodiment, the precursor is printable and is in the form of a printing ink or printing paste for coating a printed field effect transistor (FET), preferably a thin film transistor (TFT).
The term “printable precursor” is taken to mean a precursor material that, due to its material properties, can be processed by a printing process from the wet phase. During the printing process, printing ink or printing paste is transported from the storage container to the substrate, depending on the printing process.

Thus, the precursor material has a viscosity and stability during the printing process suitable for the printing process, and is suitable for conversion to this type of printing ink or printing paste with suitable wettability and adhesion to the substrate. Must be possible.
Experience shows that different viscosity ranges of inks or pastes are preferred for different printing processes; for example, 1-5 mPa · s for ink jet printing (thermal), 5-20 mPa · s for ink jet printing (piezo). The gravure printing is 50 to 200 mPa · s, the flexographic printing is 50 to 500 mPa · s, and the screen printing is 2000 to 40,000 mPa · s.

  As already described above, the precursors comprise organometallic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complexes with at least one ligand from the oximate class. According to the present invention, the ligand of aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complex is 2- (methoxyimino) alkanoate, 2- (ethoxyimino) alkanoate or 2- (hydroxyimino) It is preferable to contain an alkanoate. The ligand is synthesized by condensation of alpha-keto acid or oxocarboxylic acid with hydroxylamine or alkylhydroxylamine in an aqueous or methanolic solution in the presence of a base.

The precursor or aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complex is an oxocarboxylic acid in the presence of a base such as tetraethylammonium bicarbonate or sodium bicarbonate at room temperature. Reaction with at least one hydroxylamine or alkylhydroxylamine, followed by inorganic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin salts, such as aluminum nitrate nonahydrate, Gallium nitrate hexahydrate, anhydrous neodymium trichloride, ruthenium trichloride hexahydrate, magnesium nitrate hexahydrate, oxozirconium chloride octahydrate, oxohafnium chloride octahydrate, anhydrous indium chloride Generated by the addition of such presence and / or tin chloride pentahydrate. Alternatively, in the presence of at least one hydroxylamine or alkylhydroxylamine, an oxocarboxylic acid can be formed of magnesium, hafnium or zirconium, for example hydromagnesite Mg ₅ (CO ₃ ) ₄ (OH) ₂ .4H ₂ O. Can be reacted with hydroxocarbonate.

  The oxocarboxylic acids that can be used are representative of all of this class of compounds. However, preference is given to using oxoacetic acid, oxopropionic acid or oxobutyric acid.

  Thermal conversion of aluminum, gallium, neodymium, magnesium, hafnium or zirconium complex precursors into functional aluminum oxide, gallium oxide, neodymium oxide, magnesium oxide, hafnium or zirconium oxide layers with insulating properties, or ruthenium complex precursors Is converted to a ruthenium oxide layer at a temperature of ≧ 80 ° C. The temperature is preferably 150 to 200 ° C.

Thermal conversion of the indium and tin complex precursors to a functional indium tin oxide layer having conductive properties is performed at a temperature of ≧ 150 ° C. The temperature is preferably 150 to 250 ° C.
Thermal conversion of indium, gallium and zinc complex precursors into a functional indium gallium zinc oxide layer having semiconductor properties is performed at a temperature of ≧ 150 ° C. The temperature is preferably 150 to 250 ° C.
Thermal conversion of the zinc and tin complex precursor to a functional zinc tin oxide layer having semiconductor properties is performed at a temperature of ≧ 150 ° C. The temperature is preferably 150 to 250 ° C.

  Conversion of an aluminum, gallium, neodymium, magnesium, hafnium or zirconium complex precursor to a functional aluminum oxide, gallium, magnesium, hafnium or zirconium layer with insulating properties, or conversion of a ruthenium complex precursor to ruthenium oxide, or Conversion of indium and tin complex precursors into functional indium tin oxide layers with conductive properties, or conversion of indium-gallium-zinc and tin complex precursors into functional oxide layers with semiconductor properties, etc. In a preferred embodiment, the irradiation is performed by irradiating with UV light having a wavelength of <400 nm.

  The wavelength is preferably 150 to 380 nm. The advantage in the case of UV irradiation is that the aluminum oxide, gallium oxide, neodymium oxide, ruthenium oxide, magnesium oxide, hafnium oxide, zirconium oxide, indium tin oxide and indium gallium zinc oxide or zinc tin oxide layer produced thereby are Having a reduced surface roughness. This is a risk that the increased roughness of the surface does not allow these layers to be formed uniformly for subsequent thin layers and is therefore not electrically functional (eg, a short circuit due to a damaged dielectric layer). This will mean an increase.

Aluminum oxide, gallium oxide, neodymium oxide, magnesium oxide, hafnium oxide or zirconium oxide layers produced from the corresponding precursors exhibit a breakdown voltage of> 0.1 MV / cm between the two conductors. Preferred is a breakdown voltage of 1 to 10 MV / cm.
The breakdown voltage can be determined by the measurement and evaluation methods described in DIN EN ISO 2376: 2009-07.
The indium tin oxide layer (ITO layer) preferably has a resistivity (determined by four-point measurement) of <10 ⁻³ ohm · cm. A specific resistance of 10 ⁻³ to 10 ⁻⁵ ohm · cm is preferred.
The conductivity can be determined by the direct current four probe method. This measurement method is described in DIN 50431 or ASTM F43-99.

The indium gallium zinc oxide (IGZO) layer or the zinc tin oxide (ZTO) layer preferably has a charge carrier mobility of> 10 ⁻³ cm ² / Vs. Preferred is a charge carrier mobility of 0.1 to 10 cm ² / Vs.
The characterization and determination of the parameters of the semiconductor material can be performed by the measurement and evaluation methods described in IEEE 1620.

  The present invention further comprises one or more functional layers in a field effect transistor of the organometallic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complex or precursor of the present invention. Relates to use for manufacturing.

  In accordance with the present invention, the substrate is a rigid substrate, such as, for example, a glass, ceramic, metal or plastic substrate, or a flexible substrate, and in particular can be either a plastic film or a metal foil. In accordance with the present invention, a flexible substrate (film or foil) is preferably used.

  Application of the precursor solution of the invention to a substrate by methods such as dip coating, spin coating and ink jet printing or flexographic / gravure printing is known to those skilled in the art (MA Aegerter, M. Menning; Sol-Gel). Technologies for Glass Producers and Users, Kluwer Academic Publishers, Dordrecht, Netherlands, 2004), where inkjet printing or flexographic / gravure printing is preferred according to the invention.

The term “field effect transistor (FET)” means a group of unipolar transistors (electrons or holes or electron defects depending on the design) where only one charge is involved in current transport, as opposed to bipolar transistors. To be interpreted. The most widely known type of FET is a MOSFET (metal oxide semiconductor FET).
The FET has three connections:
・ Source, gate, drain.

  In the MOSFET, there is also a fourth bulk (substrate) connection. In the case of individual transistors, this is already connected internally to the source connection and not separately.

In accordance with the present invention, the term “FET” generally encompasses the following types of field effect transistors:
・ Barrier-layer field effect transistor (JFET)
・ Schottky field effect transistor (MESFET)
・ Metal oxide semiconductor FET (MOSFET)
・ High electron mobility transistor (HEMT)
・ Ion sensitive field effect transistor (ISFET)
Thin film transistor (TFT).

  Preferred is a TFT according to the present invention, whereby large area electronic circuits can be manufactured.

The invention further relates to a printed electronic component having the following thin layers:
A hard or flexible conductive substrate, or an insulating substrate having a conductive layer (gate), a corresponding precursor, organometallic aluminum, gallium, neodymium, magnesium, hafnium containing at least one ligand from the oximate class Or an insulator containing aluminum oxide, gallium, neodymium, magnesium, hafnium or zirconium obtained from a zirconium complex; at least one electrode (drain electrode)
·semiconductor.

  The aluminum oxide, gallium, neodymium, magnesium, hafnium or zirconium layer has a thickness of 15 nm to 1 μm, preferably 30 nm to 750 nm. The layer thickness depends on the coating technique used in each case and its parameters. In the case of spin coating, these are, for example, the spin speed and time.

The invention further relates to a printed electronic component having the following thin layers:
Hard or flexible conductive with a conductive layer (gate) comprising the corresponding precursor, organometallic indium containing at least one ligand from the oximate class and indium tin oxide (ITO) obtained from a tin complex Substrate or insulating substrate / insulator / at least one electrode (drain electrode)
·semiconductor.

  The indium tin oxide layer (ITO layer) has a thickness of 15 nm to 1 μm, preferably 100 nm to 500 nm. The layer thickness depends on the coating technique used in each case and its parameters. In the case of spin coating, these are, for example, the spin speed and time.

The invention further relates to a printed electronic component having the following thin layers:
・ Hard or flexible conductive substrate or insulating substrate with conductive layer (gate) ・ Insulator ・ At least one electrode (drain electrode)
·semiconductor. The semiconductor is derived from an organometallic indium, gallium, zinc complex or a complex of zinc and tin, which is a corresponding precursor and contains at least one ligand from the oximate class, indium gallium zinc oxide (IGZO). ) Or alternatively it must consist of a multinary, amorphous phase containing zinc tin oxide (ZTO).

  The indium gallium zinc oxide (IGZO) or zinc tin oxide (ZTO) layer has a thickness of 15 nm to 1 μm, preferably 20 nm to 200 nm. The layer thickness depends on the coating technique used in each case and its parameters. In the case of spin coating, these are, for example, the spin speed and time.

  In a preferred embodiment, the electronic component described above consists of a field effect transistor or thin film transistor constructed from a gate, an insulating layer, a semiconductor and electrodes (drain and source). The gate preferably depends on the design as a thin layer or substrate material, a highly n-type doped silicon wafer, a heavily n-type doped silicon thin layer, a conductive polymer (eg polypyrrole-polyamino Benzene sulfonic acid or polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS)), conductive ceramics (eg indium tin oxide (ITO) or tin oxide doped with Al, Ga or In (AZO, GZO, IZO)) and It consists of tin oxide (FTO, ATO) doped with F or Sb) or metal (eg gold, silver, titanium, zinc). Depending on the design, the thin layer can be applied below (bottom gate) or above (top gate) the semiconductor or insulating layer being placed.

  The electronic component is preferably a polymer (eg poly (4-vinylphenol), polymethyl methacrylate, polystyrene, polyimide or polycarbonate) or ceramics (eg silicon dioxide, silicon nitride, aluminum oxide, gallium oxide, neodymium oxide, magnesium oxide, An insulating layer made of hafnium oxide or zirconium oxide).

  The electronic component is preferably a semiconductor layer made of a semiconductor organic compound (eg polythiophene, oligothiophene or polytriarylamine) or ceramics (eg zinc oxide, indium gallium zinc oxide (IGZO) or zinc tin oxide (ZTO)). Have

  The electronic component is preferably a highly thin n-type doped silicon layer, a conductive polymer (eg polypyrrole-polyaminobenzenesulfonic acid or polyethylenedioxythiophene-polystyrenesulfonic acid (PEDOT-PSS)), conductive ceramics ( For example indium tin oxide (ITO) or tin oxide doped with Al, Ga or In (AZO, GZO, IZO) and tin oxide doped with F or Sb (FTO, ATO)) or metal (eg gold, silver, Source and drain electrodes containing titanium, zinc). Depending on the design, the electrode (preferably designed as a thin layer in the present invention) can be placed below (bottom contact) or above (top contact) the semiconductor or insulating layer being placed (see FIG. See 8a and b).

  In the preferred embodiment described above, the gate, insulator and semiconductor can be applied in an unstructured manner by spin coating or dip coating or vapor phase or liquid phase deposition techniques. Furthermore, the gates, insulators, semiconductors and electrodes can be applied in a systematic manner by flexographic / gravure printing, ink jet printing or vapor deposition techniques from the gas phase or liquid phase. Preferred is a printing process according to the present invention.

The invention further relates to a method for producing an electronic structure having an aluminum oxide, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin layer or surface or mixtures thereof,
a) Any one of the inventive organometallic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complexes or mixtures thereof corresponding to the electronic structure to be achieved Or in two or more layers, applied to a substrate by dip coating, spin coating or ink jet printing or flexographic / gravure printing,

b) heating or drying the applied precursor layer in air or in an oxygen atmosphere while forming an aluminum oxide, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium, tin or indium tin layer or surface; ,
c) Finally, the applied electronic structure can be sealed by an insulating layer, which is provided with contacts and completed.

This process produces both electronic components and also compounds of individual components in an integrated circuit.
The following examples are intended to illustrate the present invention.
However, they should not be considered limiting at all. All compounds or components that can be used in the compositions are known, commercially available, or can be synthesized by known methods.

Example 1 Preparation of Magnesium Oxide Precursor, Bis [2- (methoxyimino) propanoate] Magnesium Potassium bicarbonate (12.02 g, 120 mmol) was divided into small portions and stirred in 100 ml water. Add to a solution of sodium pyruvate (6.60 g, 60 mmol) and methoxylamine hydrochloride (5.01 g, 60 mmol). When overt gas evolution is complete, the mixture is stirred for an additional 30 minutes. Magnesium nitrate hexahydrate (7.69 g, 30 mmol) is then added and the mixture is stirred for an additional hour. The clear solution is concentrated to half volume in a rotary evaporator and cooled to about 5 degrees. The white precipitate formed is filtered off and recrystallized from hot water. Yield 2.60 g (34.8%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 2: Preparation of the magnesium oxide precursor bis [2- (methoxyimino) propanoate] magnesium without alkali metal Alternatively, the following reaction procedure is possible.
Hydromagnesite (20.0 g) is added in portions to a solution of pyruvic acid (10.56 g, 120 mmol) and methoxylamine hydrochloride (10.04 g, 120 mmol) in 100 ml of water. When apparent gas evolution is complete, the mixture is stirred for 1 hour and unreacted hydromagnesite is filtered off. The clear solution is concentrated to half volume in a rotary evaporator and cooled to about 5 degrees. The white precipitate formed is filtered off and recrystallized from hot water. Yield 6.50 g (43.5%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 3: Production of an undoped magnesium oxide layer from a magnesium precursor with insulator properties (from Example 1 or 2) Magnesium oximate prepared according to Example 1 or 2 is applied to a glass, ceramic or polymer substrate. Applied by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 210 ° C. for 10 minutes. The magnesium oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of an amorphous or nanocrystalline material. The layer has insulator properties.

Example 4: Preparation of zirconium dioxide precursor, zirconium hydroxo [2- (methoxyimino) propanoate] Sodium bicarbonate (7.56 g, 90 mmol) was added to sodium pyruvate (9.90 g, 90 mmol) in 100 ml water. And a solution of methoxylamine hydrochloride (7.53 g, 90 mmol) in small portions and added with stirring. When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of zirconium tetrachloride (5.24 g, 22.5 mmol) in 125 ml of tetrahydrofuran is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of n-hexane, filtered off and dried in a desiccator. Yield 3.50g. The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 5 Production of Zirconium Oxide Layer from Zirconium Dioxide Precursor Zirconium oximate prepared according to Example 4 is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The zirconium oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of an amorphous or nanocrystalline material. The layer has insulator properties.

Example 6: Preparation of Hafnium Hydroxo [2- (methoxyimino) propanoate], a Hafnium Dioxide Precursor Sodium bicarbonate (7.56 g, 90 mmol) was divided into small portions with stirring in 100 ml water. Add to a solution of sodium pyruvate (9.90 g, 90 mmol) and methoxylamine hydrochloride (7.53 g, 90 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of hafnium tetrachloride (7.21 g, 22.5 mmol) in 125 ml of tetrahydrofuran is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of n-hexane, filtered off and dried in a desiccator. Yield 4.75g. The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 7 Production of Hafnium Oxide Layer with Insulator Properties Hafnium oximate prepared according to Example 6 is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The hafnium oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of an amorphous or nanocrystalline material. The layer has insulator properties.

Example 8: Preparation of aluminum oxide precursor, tris [2- (methoxyimino) propanoate] aluminum Sodium bicarbonate (1.68 g, 20 mmol) was divided into small portions and stirred with stirring in 50 ml of water. Add to a solution of sodium pyruvate (2.20 g, 20 mmol) and methoxylamine hydrochloride (1.67 g, 20 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of aluminum nitrate nonahydrate (2.50 g, 6.6 mmol) in 125 ml of methanol is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 50 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of n-hexane, filtered off and dried in a desiccator. Yield 1.12 g (45.30%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 9: Production of an aluminum oxide layer having insulator properties Aluminum oximate prepared according to Example 8 is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The aluminum oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of a nanocrystalline material. The layer has insulator properties.

Example 10 Preparation of Tris [2- (methoxyimino) propanoato] gallium, a gallium oxide precursor Sodium bicarbonate (1.68 g, 20 mmol) was divided into small portions and stirred in 50 ml of water. Add to a solution of sodium pyruvate (2.20 g, 20 mmol) and methoxylamine hydrochloride (1.67 g, 20 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of gallium nitrate hexahydrate (2.40 g, 6.6 mmol) in 125 ml of methanol is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of n-hexane, filtered off and dried in a desiccator. Yield 0.96 g (34.82%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 11 Production of Gallium Oxide Layer with Insulator Properties A gallium oximate prepared according to Example 10 is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The gallium oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of a nanocrystalline material. The layer has insulator properties.

Example 12 Preparation of Tris [2- (methoxyimino) propanoato] neodymium, a Neodymium Oxide Precursor Sodium bicarbonate (1.68 g, 20 mmol) was divided into small portions and stirred in 50 ml of water. Add to a solution of sodium pyruvate (2.20 g, 20 mmol) and methoxylamine hydrochloride (1.67 g, 20 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of anhydrous neodymium trichloride (1.65 g, 6.6 mmol) in 125 ml of methanol is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of n-hexane, filtered off and dried in a desiccator. Yield 1.55 g (47.83%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 13: Production of a neodymium oxide layer having insulator properties Neodymium oximate prepared according to Example 12 is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The neodymium oxide film thus obtained is uniform, has no cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of a nanocrystalline material. The layer has insulator properties.

Example 14 Preparation of Tris [2- (methoxyimino) propanoato] ruthenium, a Ruthenium Oxide Precursor Sodium bicarbonate (1.68 g, 20 mmol) was divided into small portions and stirred with stirring in 50 ml of water. Add to a solution of sodium pyruvate (2.20 g, 20 mmol) and methoxylamine hydrochloride (1.67 g, 20 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of ruthenium trichloride hexahydrate (2.08 g, 6.6 mmol) in 125 ml of methanol is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of toluene, filtered off and dried in a desiccator. Yield 1.34 g (45.33%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 15: Production of a ruthenium oxide layer A ruthenium oximate prepared according to Example 14 is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The ruthenium oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of a nanocrystalline material.

Example 16: Dielectric Layer Fabrication The example illustrates the fabrication of a dielectric layer. A layer of zirconium oxide is applied to a highly doped n-type conductive silicon wafer by spin coating or printing, followed by baking at 200 ° C. for 10 minutes or UV irradiation at 150 mW / cm ^{2 for} 15 minutes. To form. After applying the counter electrode, the breakdown voltage value for the dielectric layer can be determined to be 1 MV / cm.

Example 17: Fabrication of Thin Film Transistor The example shows a field effect transistor (FET) according to Figures 8a and 8b. The part consists of a highly n-doped silicon wafer with a dielectric layer applied. Next, a semiconductor layer is made, followed by a metal electrode structure made by metal deposition or metal ink printing (FIG. 8a). Alternatively, the electrode structure can be made first, followed by the semiconductor layer (FIG. 8b).

Example 18: Preparation of indium oxide precursor, tris [2- (methoxyimino) propanoate] indium Sodium bicarbonate (1.68 g, 20 mmol) was divided into small portions in 50 ml water with stirring. Add to a solution of sodium pyruvate (2.20 g, 20 mmol) and methoxylamine hydrochloride (1.67 g, 20 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of anhydrous indium chloride (1.95 g, 6.6 mmol) in 125 ml of methanol is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of dichloromethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of n-hexane, filtered off and dried in a desiccator. Yield 1.80 g (58.9%). The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 19: Preparation of tin oxide precursor, tin hydroxo [2- (methoxyimino) propanoate] Sodium bicarbonate (7.56 g, 90 mmol) was divided into small portions and stirred in 100 ml water. Add to a solution of sodium pyruvate (9.90 g, 90 mmol) and methoxylamine hydrochloride (7.53 g, 90 mmol). When apparent gas evolution is complete, the mixture is stirred for an additional 30 minutes. The mixture is then completely evaporated to dryness in a rotary evaporator. A solution of anhydrous tin chloride pentahydrate (7.88 g, 22.5 mmol) in 250 ml of methanol is added to the white powder thus obtained and the mixture is stirred for 2 hours. The solution is filtered and evaporated to dryness in a rotary evaporator. The residue is taken up in 100 ml of acetone or dimethoxyethane and the suspension thus obtained is filtered again. The product is then precipitated from the filtrate using a large amount of diethyl ether, filtered off and dried in a desiccator. Yield 3.7g. The compounds thus obtained can be characterized by IR and NMR spectroscopy.

Example 20: Production of Indium Tin Oxide (ITO) Conductive Layer Indium and tin oximate prepared according to Examples 18 and 19 were dissolved together in a 90:10 molar ratio and spin coated onto a glass, ceramic or polymer substrate ( Or by dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 60 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 1 hour. The indium tin oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of an amorphous or nanocrystalline material. The layer has electrical conductivity.

Example 21 Production of Semiconductor Layer of Indium Gallium Zinc Oxide (IGZO) Indium and / or gallium oximate and zinc oximate prepared according to Examples 10 and 18 (from JJ Schneider et al. Advanced Materials, 2008, 20, 3383-3387 Is obtained in a suitable molar ratio. Suitable molar ratios for the preparation of the semiconductor phase are given in H. Hosono, Journal of Non-Crystalline Solids 2006, 352, 851-858; thus, for example, indium: gallium: zinc = 1: 1: 1 or indium : Zinc = 2: 3.

The solution thus obtained is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The indium gallium zinc oxide film thus obtained is uniform, has no cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of an amorphous material. The layer has semiconductor characteristics.

Example 22: Preparation of zinc tin oxide (ZTO) semiconductor layer Tin oximate and zinc oximate prepared according to Example 19 (obtained by the method of JJ Schneider et al. Advanced Materials, 2008, 20, 3383-3387) Dissolve together in a suitable ratio. For example, a tin content of 0-30 mol percent Sn / (Sn + Zn) is suitable. The solution is applied to a glass, ceramic or polymer substrate by spin coating (or dip coating or also ink jet printing). The coating is then heated in air at a temperature above 200 ° C. for 10 minutes or it is irradiated with UV at 150 mW / cm ^{2 for} 15 minutes. The zinc tin oxide film thus obtained is uniform, free of cracks and exhibits a non-porous surface morphology. Depending on the firing temperature, the layer consists of an amorphous or nanocrystalline material. The layer has semiconductor characteristics.

Examples 23-26: Description of various coating processes In all cases, a solution of 10-20 weight percent precursor compound is used. Suitable solvents are 2-methoxyethanol, 2-butanol, methanol, dimethylformamide or mixtures thereof.
The viscosity of the printing ink can be determined using a rheometer such as Haake's MARS Rheometer. The decision is made under standard environmental conditions (DIN 50 014-23).

Immersion coating: Pulling speed is about 1 mm / second. The substrate used is a 76 × 26 mm glass plate.
Spin coating: For spin coating, 150 μl of solution is applied to the substrate. The substrate used is 20 × 20 mm quartz or 15 × 15 mm silicon (having gold electrodes for the manufacture of FETs). The parameters selected for time and speed are 10 seconds at an initial speed of 1000 rpm and 20 seconds at a final speed of 2000 rpm.

Inkjet printing: The printing process can be performed using a Dimatix Dimatix DMP 2831 printer. The printing ink used is a 10 weight percent solution of hafnium hydroxo [2- (methoxyimino) propanoate], a hafnium oxide precursor, in diethylene glycol monoethyl ether, which has a pore size of 0.2 μm. It is introduced using a syringe filter having a size. The film can be printed on a substrate such as glass with an indium tin oxide coating (Merck) and converted to ceramics by subsequent UV irradiation (Fe-doped Hg lamp; irradiation time: 400 mW / cm ² 4 minutes).

Flexo printing: The printing process can be performed using an IGT F1 unit from IGT Testing Systems.
The printing ink used is a 10 weight percent solution of hafnium hydroxo [2- (methoxyimino) propanoate], a hafnium oxide precursor, in methoxyethanol. 1 ml of solution is applied manually to the contact zone.

The following printing parameters are selected for the knife coating sheet / anilox roll:
・ Anilox roll / plate cylinder contact pressure 10N
・ Plate cylinder / back pressure cylinder contact pressure 10N
・ Printing speed 0.8m / s
-Printing plate: full-tone surface, 90% ink coverage (area coverage)
・ Anilox roll absorption volume 20ml / m ²

Full-range printing can be achieved on a substrate such as silicon or quartz. The precursor can then be converted to ceramics by UV irradiation (Fe-doped Hg lamp; irradiation time: 7 minutes at 400 mW / cm ² ).

Claims (16)

  Precursors for coating electronic components, containing at least one ligand from the oximate class, organometallic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin complexes or Said precursor comprising a mixture thereof.   Precursor according to claim 1, characterized in that the ligand is 2- (methoxyimino) alkanoate, 2- (ethoxyimino) alkanoate or 2- (hydroxyimino) alkanoate.   Precursor according to claim 1 or 2, characterized in that it is printable and used in the form of a printing ink or printing paste in a printed field effect transistor (FET). The following thin layers:
A hard or flexible conductive substrate, or an insulating substrate having a conductive layer (gate). Aluminum oxide, gallium, neodymium, magnesium, hafnium obtained from the corresponding precursor according to any one of claims 1 to 3. Insulator containing zirconium and at least one electrode (drain electrode)
-Printed electronic parts with semiconductors. The following thin layers:
A hard or flexible conductive substrate or an insulating substrate / insulator having a conductive layer (gate) containing indium tin oxide (ITO) obtained from the corresponding precursor according to claim 1. At least one electrode (drain electrode)
-Printed electronic parts with semiconductors. The following thin layers:
・ Hard or flexible conductive substrate or insulating substrate with conductive layer (gate) ・ Insulator ・ At least one electrode (drain electrode)
A printed electronic component having a semiconductor comprising indium gallium zinc oxide (IGZO) or zinc tin oxide (ZTO) obtained from the corresponding precursor according to claim 1.   7. The substrate according to any one of claims 4 to 6, characterized in that the substrate can be either a hard substrate, for example a glass, ceramics, metal or plastic substrate, or a flexible substrate, in particular a plastic film or a metal foil. Printed electronic components as described.   The method for producing a precursor according to any one of claims 1 to 3, wherein at least one oxocarboxylic acid is reacted with at least one hydroxylamine or alkylhydroxylamine in the presence of a base. Said method, characterized in that inorganic aluminum, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin salts or mixtures thereof are subsequently added.   9. Process according to claim 8, characterized in that the oxocarboxylic acid used is oxoacetic acid, oxopropionic acid or oxobutyric acid. A method for producing an electronic structure having an aluminum oxide, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin layer or surface or mixtures thereof,
a. Electronic structure to achieve a precursor solution comprising an organometallic aluminum, magnesium, gallium, neodymium, ruthenium, hafnium, zirconium, indium and / or tin complex or a mixture thereof according to any one of claims 1-3 Applying to the substrate by dip coating, spin coating or ink jet printing or flexographic / gravure printing in any one or more layers corresponding to the body,
b. The applied precursor layer is heated or dried in air or in an oxygen atmosphere while forming an aluminum oxide, gallium, neodymium, ruthenium, magnesium, hafnium, zirconium, indium and / or tin layer or surface or a mixture thereof. ,
c. Finally, the applied electronic structure can be sealed by an insulating layer, provided with contacts and completed.
And said method.   The method according to claim 10, wherein the temperature during heating is T ≧ 80 ° C.   The method according to claim 10, characterized in that the heating or drying is performed by irradiating with UV light having a wavelength of <400 nm.   The aluminum oxide, gallium oxide, neodymium oxide, ruthenium oxide, magnesium oxide, hafnium oxide or zirconium oxide layer has a breakdown voltage of> 0.1 MV / cm between the two conductors. The method as described in any one of 10-12. 13. The method according to claim 10, wherein the indium tin oxide layer (ITO layer) has a specific resistance of <10 ⁻³ ohm · cm, determined by four-point measurement. . The indium gallium zinc oxide (IGZO) layer or the zinc tin oxide (ZTO) layer has a charge carrier mobility of> 10 ⁻³ cm ² / Vs, according to claim 10. The method according to item.   Use of the precursor according to any one of claims 1 to 3 for the production of one or more functional layers in a field effect transistor.

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